Professional Documents
Culture Documents
0350 820X1703247R
0350 820X1703247R
________________________________________________________________________
doi: https://doi.org/10.2298/SOS1703247R
Abstract:
The limestone, as an economically sustainable and easily available basic raw
material, is frequently utilized in the building industry for resolving of the environmental
protection issues. The limestone is incorporated in a cementitious system either by grinding
with cement clinker, or by blending with the binder during concrete production. The
employing of powdery limestone as partial cement replacement gives the construction
composites with properties comparable to that of conventional concrete. The study of
limestone thermal behavior and its chemistry is crucial for the prognosis of the designed
composites properties. In this work, the instrumental techniques (atomic emission
spectroscopy, differential thermal and thermo-gravimetric analysis, Fourier transform
infrared spectroscopy) and the Principal component analysis were employed to discriminate
and classify 22 limestone types. The PCA statistical method, as a means of spectra and
experimental data fingerprinting, grouped the samples in a multi-dimensional factor space
producing four graphical prognosis - one for each instrumental method. DTA/TG peak values
varied the most in a short range between 830-870 °C, while FTIR spectra showed the highest
diversity in the 867-887 cm-1 and 1237-1647 cm-1 ranges. This research was governed by an
idea to reveal whether it is possible to differentiate various limestone types and to predict the
possibility of their employment in construction composites on the basis of the results of
instrumental and mathematical analyses.
Keywords: Thermal behavior; Chemical analysis; Microstructure; FTIR; DTA/TG; SEM;
Binder; Filler.
1. Introduction
(e.g. kaolinite, hydrous mica, montmorillonite) are other two major constituents of the
limestone [1]. Since a substitution of calcium by magnesium occasionally occurs, a limestone
that contains 5-35 % of Mg is defined as “magnesian limestone”. If Mg content is below 5 %,
the rock is classified as a “high-calcium limestone” [2]. The carbonates present in the
limestone customarily appear as calcite, aragonite and/or vaterite mineral phases. However,
the only crystal form of real significance is calcite [3]. By being the most abundant and
enclosing at least 50 % of all present mineral phases in the limestone, calcite is an important
resource and subject of investigations in various scientific fields: mineralogy, chemistry,
physics, materials science [4-7]. The crystalline structure of calcite is commonly illustrated by
the R3c trigonal space group [8]. Due to the perfect rhombohedral cleavage, calcite exhibits a
small value of Mohs hardness (3.0). The specific gravity of calcite is 2.7 [3]. The thermally
induced behavior, i.e. calcium carbonate stability constrains and the rules of phase transitions,
represents a basis for a comprehensive study of the limestone [9-11]. Due to the alternations
in carbonate mineral phases at different temperatures, materials of diverse compositions can
be obtained for use in a variety of applications.
Limestone is an economically sustainable and easily available resource; therefore,
both in its crude and powdery form, the limestone can be readily produced and utilized [12].
Natural limestone minerals are the basic raw materials for building industry and for resolving
of the environmental protection issues [1]. Namely, the limestone is extensively employed in
the interior and exterior as architectural stones and walls, in the production of lime (CaO), as
coarse aggregates and fillers in construction composites (concretes and mortars), in paint and
polymer fabrication as fillers, as metallurgical flux, in road building (aggregates for highways
and runways, railroad ballasts, embankments, soil stabilization agents) [13-15]. Since the
limestone is able to decrease the CO2 footprint of concrete by approximately 15 %, it became
one of the base materials used in the manufacturing of Portland cement (PC) and one of the
most common mineral additions with low reactivity [12, 16].
The application of powdery limestone as partial cement replacement gives the
construction composites with properties comparable to that of conventional concrete [17]. The
limestone incorporation in cementitious systems is performed either by limestone grinding
with the PC clinker, or supplementary blending of PC with limestone powder during concrete
production [18]. The first method results in the composite system with a finer limestone
phase, while the second method produces a material with a precisely controlled limestone
grain-size distribution. The grinded limestone accelerates hydration reactions, amends the
particles packing, induces the carboaluminates formation that decreases the overall pore
volume, and finally results in minimized strength loss associated with limestone [18]. The
blended limestone influences the cementitous composite through a series of physical and
chemical impacts. Used as an additive in the concrete design, the limestone enhances the
viscosity, increases the workability and improves the flowability of a green mixture by
causing alternations in particle size, heterogeneous nucleation and dilution (reduced
coagulation and increased clinker particle dispersion). Also, the inclusion of the limestone is a
prerequisite for reduction of the initial and final concrete setting times followed by a minimal
increase in total shrinkage in comparison with the conventional concretes [17]. The chemical
influence relates to the cement hydration and the reaction of limestone with calcium
aluminate to form calcium mono-carboaluminate [19]. The addition of the limestone powder
leads to the premature cement hydration and supplies nucleation sites for the C-S-H gel
formation. The cementitous composite early-age mechanical properties are enhanced due to
the promoting impact that limestone powder has on the cement hydration, while final
strengths are reduced because of the dilution effect [12].
The study of the thermal decomposition reactions of limestone minerals and the
chemistry of the limestone constituents is relevant for the analysis and prognosis of the
properties and behavior of designed construction composites and the assessment of their
engineering and industrial application possibilities [2, 19-21]. In this work, differential
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 249
___________________________________________________________________________
thermal analysis (DTA), thermo-gravimetric analysis (TGA) and Fourier transform infrared
spectroscopy (FTIR) were employed to characterize and discriminate 22 different limestone
types. The chemical characteristics of the examined representative samples were also
observed. All three instrumental methods (DTA, TGA and FTIR), as well as the chemical
analysis, were combined with the Principal component analysis (PCA) to classify the samples.
This research was governed by an idea to reveal whether it is possible to differentiate various
limestone types and to predict the possibility of their employment in construction composites
on the basis of the results of the conducted instrumental and mathematical analyses.
The limestone samples that were used in this study originate from twenty-two
different deposits located on the territories of Republic of Serbia and Montenegro. The
investigated ore is classified as a sedimentary calcite rock. The crude limestone samples were
collected from each deposit, taking into account the differences in the macroscopic
composition of the stone in order to be fully representative. Representative ore samples of 50
kg, obtained from each deposit according to the standard ore sampling campaign [22, 23]
were used in the investigation. After the initial rough crushing via primary jaw crusher (KHD
Humboldt Wedag; Model 5"x 6") and secondary cone crushing (Denver Roll Crusher; Model
6"x10", size: 10 mesh/1.651 mm), the samples were split and bagged in 5 kg sub-samples.
The sub-samples were further pulverized for the laboratory analyses in an agate stone mill
(KHD Humboldt Wedag), and subsequently packed in the plastic bags and marked as K1-22.
The chemical analysis of the limestone samples was performed by atomic emission
spectroscopy (AES) on a PinAAcle 900 instrument (Perkin Elmer, USA). The five samples,
per each limestone type (K1-22), were acquired by cone & quartering method from a 5 kg
sub-sample. Representative samples (100g) were pulverized in a laboratory mill prior to the
testing, which was conducted in accordance with the standard methods for chemical analyzing
(ASTM C25/C1271/C1301) [24-26] The loss on ignition (LoI) was determined as a weight
difference between 20° and 1000 °C. The acquired averaged values of the main oxides are
presented in the Table I. The determined pH values for all limestone samples were above 9.0
making them very strong alkaline [27].
The Principal component analysis (PCA), as the main tool in exploratory data
analysis, is applied to classify the limestone samples (K1-22) on the bases of the results
acquired via instrumental techniques (AES, DTA, TG, and FTIR). This statistical method has
been frequently used for fingerprinting of the spectra and/or experimental and instrumentally
obtained data of similar samples. It is a multivariate technique where data are transformed
into orthogonal components which are linear combinations of the original variables. TGA and
DTA peak values, and FTIR and AES spectra reflections were thoroughly examined to show
the possible dissimilarities between obtained samples. PCA is performed by Eigenvalue
decomposition of a data correlation matrix [28]. All samples were grouped in a multi-
dimensional factor space and four PCA graphics were plotted, according to the results of the
TG, DTA, FTIR and the chemical analysis (AES) of the investigated limestone samples. The
PCA decomposes the original matrix into several products of multiplication into loading
(different samples) and score (TG, DTA, FTIR and AES results) matrices. Different samples
subjected to different testing conditions were taken as variables (column of the input matrix),
while the results of the TG, DTA, FTIR and AES were regarded as mathematical cases (rows
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 251
___________________________________________________________________________
of the matrix). The analysis, in which the first component has the largest possible variance in
the transformation, is used to achieve maximum separation between parameter clusters [29,
30]. This approach, evidencing spatial relationship between processing parameters, enabled
discrimination between various samples. Descriptive data analysis, i.e. PCA, was performed
via software package STATISTICA 10.0 (StatSoft Inc., Tulsa, OK, USA) [31].
The primary constituent of all investigated limestone samples (K1-22) was calcium
carbonate (CaCO3), with its content set at approximately 95 %. The lowest CaCO3 content
was detected in K5 sample (92.93 %), while the highest CaCO3 percentage was present in
K19 sample (99.09 %). High loss on ignition (LoI) also refers to the presence of calcium
carbonate as the main combustible component, but also implies the inclusion of clay minerals
in limestone mineralogical conformation. With an average value of 55 %, CaO is the principal
chemical compound detected by AES technique (chemical analysis results are provided in
Tab. I). The investigated limestone also contained Al2O3, SiO2, MgO, Fe2O3, Na2O, K2O,
TiO2 and P2O5 as minor constituents. The content of each of previously mentioned oxides was
below 1 %, except MgO whose portion showed the increased value in the chemical analyses
of the samples K2 (1.04 %), K4 (1.40 %), K5 (3.61 %), K7 (1.08 %) and K8 (1.61 %). The
Principal component analysis (PCA) of the acquired AES results (major and minor
constituents) is illustrated in the Fig. 1.
Fig. 1. PCA biplot for the results of the chemical analysis of K1-22 limestone samples.
Since the limestone is identified and utilized as a cement addition and a replacement
in PC clinker blends and as a mineral admixture in the design of construction composites (e.g.
mortars and concretes), detecting and monitoring its chemical composition is of the uttermost
importance. Namely, maintaining the CaO content as high as possible is crucial in order to
induce early cement hydration. Thereby, the supplementary nucleation sites for the formation
of continuous layer of calciumcarbosilicate hydrates (C-S-H gel) are provided [12]. Their role
is to bind together the cement particles into a cohesive composite structure. Additional CaCO3
amount also induces the formation of calcium carboaluminates which are accounted important
for the development of construction composites mechanical strengths [32, 33]. The detected
CO2 content in the investigated limestone samples meagerly varied from 43.13 % (K12) to
44.18 % (K8). Keeping the carbon dioxide portion fixed is important for the limestone
application in the cement and concrete production where maintaining the CO2 emission as low
as possible in one of the major environmental protection imperatives [34, 35]. The chemical
limits regarding the presence of magnesium, sulfur and alkalis (Na, K) are rigorously
252 D. Radulović et al. /Science of Sintering, 49 (2017) 247-261
___________________________________________________________________________
regulated for the application of limestone in cement clinker production [36]. The detected
quantity of chemical constitutes are always evaluated to assess the feasibility of limestone
application in construction composite materials such as concrete and mortar. MgO content is
monitored due to the proposed limitation in the cement production standards and because of
the risk related to the unsoundness of concrete. The average MgO share that is currently being
applied in EU clinker plants is set at 1.05 %, but generally the tolerated maximal MgO
content, that does not induce cement deterioration, is between 4.0 % and 6.0 % [36]. The
investigated limestone samples are being categorized as high-calcite raw materials, instead of
being dolomite rich, therefore the elevated MgO content is detected only in the three samples:
K4, K5 and K8. Also an additional limitation has to be set for the MgO and Fe2O3 ratio
because both oxides behave as fluxes. This ratio (the ratio in the cement clinker should not
surpass 1.4 [36]) reduces the possibility of melting and the formation of the defects in the
produced material. The Fe2O3 content in all samples is below 0.1 % and sulfur content is
minor (approximately 0.01 %). The concentrations of trace elements, which belong to four
categories depending on their origin and pattern of distribution [37], are also limited. Namely,
the average content of Cd, Cr, Cu, Mn, Ni, Pb, and Sb that is tolerated in a limestone-cement
composition is: 0.6, 36, 32, 706, 36, 34, and 4 ppm, respectively [36, 37]. The detected
maximal concentrations of trace elements in the K1-22 limestone samples were: Cd = 0.55
ppm; Cr = 10 ppm; Cu = 29 ppm, Mn = 35 ppm, Ni = 24 ppm, Pb = 25 ppm, and Sb = 2.5
ppm. All obtained maximal values are lower than appropriate average concentrations reported
for the limestone-cement.
As it is illustrated via PCA biplot for the results of AES analysis in Fig. 1, the first
principal component (PC1) explained 33.91 % of the total variance, i.e. the first Eigenvalue
equals 7.45. The second principal component (PC2) explained 16.26% of the total variance,
i.e. Eigenvalue equals 3.50. The maximum of Fe2O3, Cu, Cd, Ni, Cr, P, Cr, CO2, P, P2O3 and
LoI were observed for samples K8-10 which are located in the right lower corner of the
diagram. Therefore, the samples K8-10 are prone to the formation of solid solutions during
exposure to elevated temperatures due to high Fe2O3 content. The K5 sample is located in the
upper right corner of the diagram, and it has the maximal MgO content which is related to
presence of dolomite in its mineralogical composition. The K5 has been previously marked as
the sample with the lowest CaCO3 content. High Al2O3 and Na2O contents were found in the
samples K1-4 and K7 (all positioned on the right side of the graph). High SiO2, Pb and S
percentages were found in the samples K6 and K12-16 (situated on the upper left side of the
graph), while the maximal K2O, CaO and CaCO3 contents were noticed in the samples K17-
22 (lower left side of the graph). The provided chemical and PCA analyses indicated the K19
sample as the optimal limestone due to the high CaCO3 content and low percentage of Fe2O3
and MgO.
The X-ray powder diffraction patterns of K5 and K19 limestone, as the samples with
the most diverse chemical compositions, were obtained and compared in the Fig. 2 (a and b).
The XRD diagrams indicate that the investigated limestone samples are mainly
composed of calcite with minor amounts of dolomite, quartz, mica, and clay minerals. The
minor phases can scarcely be distinguished on the diagrams because their reflections are
either too feeble or overlapped and superposed by other more significant peaks. As it can be
seen in Fig. 2, the K5 sample contains the highest amount of dolomite (CaMg(CO3)2), which
is illustrated by small but visible reflections: main dolomite peak is located at 30.89°, and it is
followed by two small reflections at 41.06° and 51°. This difference in the mineralogical
composition of K5 limestone is in consistency with the chemical analysis (Tab. I), i.e. the K5
sample contained the highest percentage of MgO. In all investigated samples, the calcite was
found to be the most abundant; therefore the most significant XRD reflections belong to this
mineral phase. According to the chemical analysis, the calcium carbonate content varied from
a low of 92.93 % for the K5 sample to a high of 99.09 % for the K19 sample. One of the main
diversities between these two limestone samples is reflected in the intensities of their calcite
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 253
___________________________________________________________________________
XRD peaks. Namely, the calcite peak of K19 limestone situated at 30° is approximately 300
arbitrary units higher than adequate peak of K5 sample. Also, the higher K19 crystallinity
indicates presence of less amorphous solid. The K19 limestone has the highest calcite content,
thusly it can be considered as a suitable resource for Portland cement manufacturing.
1800
C
1600
a C C- calcite
1800 b C- calcite
D-dolomite
1600
1400
1400
1200
1200
1000
1000
800
800
600
600
400
400
C C CC
C C CC C
200 C C C
200
C C
D D
C
D
0 0
5 10 15 20 25 30 35 40 45 50 55 60 65 5 10 15 20 25 30 35 40 45 50 55 60 65
o
2θ ( ) o
2θ ( )
Fig. 2. XRD diffractogram of: a) K5 limestone sample; and b) K19 limestone sample.
a b
The dominant thermally induced reaction that took place in the investigated limestone
samples, which contained over 90 % of calcium carbonate, is calcination, i.e. decomposition
of CaCO3 induced by an exposure to strong heat. This reaction is important for the industrial
application of limestone, primarily the cement production [2, 40]. In principle, CaCO3
decomposes to lime (Eq. 1) if the ambient partial CO2 pressure is below the equilibrium value
of the partial pressure at a given temperature.
254 D. Radulović et al. /Science of Sintering, 49 (2017) 247-261
___________________________________________________________________________
Fig. 4. Variables of limestone samples projection on the first factor plane, based on DTA
peaks.
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 255
___________________________________________________________________________
The analysis of the thermally induced dissimilarities in the limestone samples was
conducted by means of the PCA. The DTA and TG output data acquired on the investigated
samples K1-22 were statistically analyzed in proposed thermal interval from 650 to 900 °C
(Fig. 4 and 5). The lower temperatures were not considered because only K5 sample exhibited
DTA effects below 650 °C. The number of factors retained in the model, for proper
classification of TGA data, in original matrix was observed as loading (different samples) and
score (peak area) by application of Kaiser and Rice’s rule. This criterion retained only
principal components with Eigenvalues higher than 1.
In the DTA data registered on the diagram (Fig. 4), the first principal component
(PC1) explained 85.77 % of the total variance, while the second principal component (PC2)
was 11.57 %. The first Eigenvalue equals 6.86. The majority of DTA effects were observed in
thermal interval from 830°-870 °C, and they were registered for the K8-22 samples. All
manifested effects were endothermic. The minimal DTA peaks were exhibited in the analyses
of the K3-5 samples. The maximal peaks were registered for the samples K1, K2, K6 and K7
in the thermal interval from 890°-900 °C.
Fig. 5. Variables of limestone samples projection on the first factor plane, based on TG peaks.
The first principal component (PC1) explained 93.35 % of the total variance (the first
Eigenvalue equals 7.47), while the second principal component (PC2) was 5.61 % in the TGA
data registered on the diagram (Fig. 5). The minimal changes in mass were observed for
samples K1-K7, which is explained by lower content of CaCO3. More significant thermally
256 D. Radulović et al. /Science of Sintering, 49 (2017) 247-261
___________________________________________________________________________
induced changes in mass were observed for the samples K8, K11-13, K15-16 and K20-21,
which comprised higher content of calcite mineral. The maximal weight changes were
registered for the samples K9-10 and K22. Most of the samples underwent changes in the
thermal interval from 830° to 880 °C, according to the PCA. Sample K19 is in the group of
moderate mass loss which highlights its high calcite content and a small percentage of
impurities in the composition.
Fourier Transform Infrared Spectroscopy (FTIR) was applied in the simultaneous
qualitative analysis of calcite as the main calcium carbonate phase found in the twenty-two
limestone samples (Fig. 6). The obtained FTIR spectra of the observed K1-22 samples were
later studied and compared using the PCA statistical analysis (Fig.7).
The FTIR measurements were conducted in the wide region of 4000-400 cm-1. The
free carbonate ion belongs to the symmetry point group D3h. Therefore, the CO32- ion has four
normal vibrations of which one belongs to the species A’1, one is of species A’2, while two
vibrations belong to the E’ species [42]. The carbonate functional group that is present in the
calcite corresponds to the D3h point group as a nonlinear with 4 atoms (N=4). This group has
3N-6=6 basic vibrations of which N-1=3 are valent [43]. The spectral difference between the
more common groups may be related to crystal structure. The spectral relationships between
the minerals of several groups are not well known, due to the complicated composition and
crystal structure. Infrared active groups of CO3, HCO3, H2O and OH normally dominate the
absorption characteristics [43].
In the FTIR spectrum of the calcium carbonates (CaCO3) the main absorption bands
appear in the regions 1500-1400 cm-1, 1100-1000 cm-1, 900-800 cm-1 and close to 700 cm-1
[42]. The infrared spectra of the calcite and dolomite groups are normally characterized by
three prominent absorption maxima and two minor peaks [43]. The analysis of the K19
sample showed eight peaks of different intensities on the diagram (given in Fig. 8): 3435,
2182, 2874, 2515, 1798, 1424, 876 and 712 cm-1. The FTIR bands at 1424, 876 and 712 cm-1
had distinguished peaks, while the rest of the peaks were minor. The registered bands are all
considered to be caused by the CO3 groups with the crystals [43]. Namely, from the analysis
of the space group characteristics, the existence of four molecular frequencies for the CO3
ions in calcite is acknowledged of which three are active in the infrared spectrum [43-45].
Since the CaCO3 contains less than one molecule of water per CaCO3 in the structure
[42], the bands that correspond to the three normal vibrations of the water molecule were
found: at 3435, 2182, 2874 and 2515 cm-1 (anti-symmetric and symmetric O-H stretches), and
at 1798 cm-1 (HOH bending). The band of medium intensity observed at 876 cm-1 is assigned
to the V2 which is a symmetric normal vibration of carbonate ion that corresponds to the CO3
out-of-plane deformation mode. The strong, broad bond at 1424 cm-1 region corresponds to
the symmetric normal V3 vibration that is an asymmetric C-O stretching mode. A relatively
weak absorption at 700 cm-1 can be related to the V4 vibration which is characterized by in-
plane deformation mode. As it can be seen in Fig. 6, the acknowledged bands are split and the
band maxima is being observed at 1424, 876 and 712 cm-1. Thereby, the site symmetry for
CO32- that is present in the limestone (i.e. calcite as the main phase) can be described as D3
(A1(R)(V1), A2(I)(V2) and E(I,R)(V3, V4)) which is in agreement with the crystalline structure
that can be determined via XRD measurements [42]. Also, a frequency value of the infrared
inactive fundamental V1 of calcite can be determined from the frequencies of two combination
bands V1+V3 and V1+V4 observed at 2515 cm-1 and 1798 cm-1, respectively, for the samples at
low temperature, resulting in the average value 1088 cm-1 for V1 which is in agreement with
the value that can be obtained from the Raman spectra of calcite [44].
The investigation of the appropriate bands for the FTIR data analysis is a difficult
task since there is a strong overlapping. Namely, the identified absorption bands that
correspond to the similar wave number may have different peak intensities (Fig 7b).
Therefore, the PCA analysis was performed on the FTIR spectra of the investigated limestone
samples (Fig.7a).
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 257
___________________________________________________________________________
a b
Fig. 7. Results of the FTIR analyses: a) variables of limestone samples projection on the first
factor plane, based on FTIR spectra; and b) comparison of the K5 and K19 FTIR spectra.
The first principal component (PC1) in the analysis explained 94.77 % of the total
variance. The first obtained Eigenvalue, in the data registered on the FTIR spectra, is equal to
42.65. The second principal component (PC2) in the FTIR data registered on the diagram was
3.99 %. The values of FTIR spectra exhibited the most profound diversities in the range 867-
887 cm-1 and afterwards in 1237-1647 cm-1 where the two main absorption bands are located.
The wave number of the third prominent peak, i.e. the band at 713 cm-1, did not significantly
varied in the observed twenty-two samples. These absorption bands located at approximately
1442, 877 and 713 cm-1 are characteristic for the CaCO3. Thereby, these results confirm the
conclusion of the XRD analysis that the samples mainly consisted of calcite mineral. The K19
sample had minimal variations from the theoretical calcite (714, 875 and 1473 cm-1 - the
vibrations of the CO32- that are characteristic for the CaCO3) which indicates that K19 has the
smallest impurities percentage in its composition.
The sample K19, which was selected as the limestone with the most appropriate
composition for the production of construction composites was submitted to the scanning
electron microphotography to acquire finer observations of the sample’s microstructure (Fig.
8).
4. Conclusion
Acknowledgements
5. References
Садржај: Кречњак је, као економична и лако доступна сировина, често употребљиван
у грађевинској индустрији у циљу разрешења проблема загађивања и заштите
животне средине. Кречњак се најчешће инкорпорира у цементни систем млевењем
заједно са цементним клинкером, или мешањем са везивом у поступку производње
бетона. Применом прашкастих кречњака, као делимичне замене за цемент, добијају се
конструкциони композити који поседују својства која су упоредива са својствима
стандардних грађевинских бетона. Изучавање термичког понашања кречњака и
његове хемије је од превасходне важности за предвиђање својстава пројектованих
композита. У овом раду су употребљене инструменталне методе (атомска емисиона
спектроскопија, диференцијално термијска и термогравиметријска анализа, и
Фуријеова трансформациона инфрацрвена спектроскопија) и Метода главих
компонената (PCA) у циљу препознавања и класификовања 22 различита типа
кречњака. PCA статистичка метода, као средство идентификовања спектра и
D. Radulović et al./Science of Sintering, 49 (2017) 247-261 261
___________________________________________________________________________
© 2016 Authors. Published by the International Institute for the Science of Sintering. This
article is an open access article distributed under the terms and conditions of the Creative
Commons — Attribution 4.0 International license
(https://creativecommons.org/licenses/by/4.0/).